Substituted bis-triazinylamino stilbene compounds and compositions thereof

ABSTRACT

Described herein are certain bis-triazinylamino stilbene type optical brighteners and their use in treating textiles and paper. The brighteners are particularly useful in conjunction with fabric softeners and in laundry detergents.

United States Patent Tscharner [451 July 11, 1972 [54] SUBSTITUTEDBIS-TRIAZINYLAMINO STILBENE COMPOUNDS AND COMPOSITIONS THEREOF [72]Inventor: Christopher Johannes Tschamer, Warwick, R.I.

Geigy Chemical Corporation, Greenburgh, NY.

[22] Filed: April 16, 1970 [2]] Appl. No.: 33,118

Related US. Application Data [62] Division of Ser. No. 561,330, June 29,1966, Pat. No.

[73] Assignee:

[52] US. Cl ..252/8.75, 117/335 T, 252/524, 252/543, 260/240 B [51] Int.Cl. ..D06m 13/46, Cl 1d 3/42 [58] Field of Search ..252/8.75, 137, 152,524,543; 260/240 13; 117/335 T [56] References Cited UNITED STATESPATENTS 3,360,470 12/1967 Wixon ..252/8.75

Primary Examiner-Herbert B. Guynn Attorney-Karl F. Jorda ABSIRACTDescribed herein are certain bis-triazinylamino stilbene type opticalbrighteners and their use in treating textiles and paper. Thebrighteners are particularly useful in conjunction with fabric softenersand in laundry detergents.

5Claims,NoDrawings SUBSTITUTED BIS-TRIAZINYLAMINO STILBENE COMPOUNDS ANDCOMPOSITIONS THEREOF This application is a division of application Ser.No. 561,330, filed June 29, 1966, now U.S. Pat. No. 3,546,218.

This invention relates to optical brightening agents and to compositionscontaining these new brightening agents.

The new compounds of this invention are optical brighteners of thebis-triazinylamino stilbene type. This class of compounds is findingrapidly increasing application in the textile, paper, detergent andother laundry product industries. The increased brightness which resultsfrom incorporating relatively minor amounts of such brighteners intopaper, textiles, detergents and other laundry products greatly enhancesthe appearance and consequently, the marketable value of the finishedproducts.

Optical brighteners improve the appearance of these products byneutralizing the familiar yellow tinge that is usually apparent inuntreated products of the type mentioned. This yellow tinge is caused bythe absorption of short wavelength light. Optical brighteners neutralizethe yellow tinge resulting therefrom by absorbing invisible ultravioletradiation and emitting the energy thereof in the form of visible blue toblue-violet light. The fluorescent properties of the op ticalbrighteners of this invention are strikingly apparent under ultravioletlight in darkroom conditions.

One area in which the full benefit of previously available opticalbrighteners has not been obtainable is in the treatment of textilefabrics, either during mill manufacturing operations or in laundries,where fabric softeners have been applied to the fabrics.

Whether the fabric softener is applied in the mill, after, or during theapplication of the brightener, or as a part of the finish cycle duringlaundering, i.e., after washing, the use of softeners has had a maskingor quenching effect on the brighteners of the prior art.

This quenching effect is noted by the decrease in brightenerfluorescence caused by a cationic softener. Thus, for example, a fabricwashed in detergent containing prior art optical brighteners willachieve a certain fluorescence level. However, if the washed fabric isthen treated with a cationic softener the fluorescence level will dropso much that practically the entire brightening affect is lost; eventhough no brightener is removed from the fabric during the applicationof the softener.

Thus the housewife may launder her family clothes with a relativelyexpensive detergent in order to achieve a brighter wash by virtue of theoptical brightener contained in the detergent, and then in finishing thewash by the routine use of a cationic fabric softener, almost completelydestroy the brightwhite affect of the brightener for which she paid apremium price in purchasing her detergent.

The new optical brightening agents which I have discovered, besidesbeing very useful for the usual applications of optical brighteners,surprisingly maintain their brightening affect on fabrics which aretreated with cationic softeners either after, or concurrently, with theapplication of the brightener agent.

The new optical brightener compounds I have discovered have thefollowing formula:

a l N 1 NCHzCHzCHzN W-NHQ-CH: L t...

wherein z hasavalueofO-l, and

X and Y each independently are: (Cl-l,) (Ol-l) (l-l) and a has a valueof 1-3,

bhasavalueofO-l,

chasavalueofO-l,

dhasavalue ofO-l. or X and Y taken together may form a morpholino ring.

The alkaline salts of the compound of the above formula are alsoencompassed within the scope of the invention. Typical basic cationsforming such salts are alkaline and alkaline earth metal cations, andcations derived from ammonia and mono-, di-, and tri-alkanolamines.

In the case of the preferred compound of this invention, X and Y bothare CH CH OH, and z has a value of 0.

Thus the preferred compound of this invention is: 4,4'-bis-4-anilino-6-[N-(3-aminopropyl)-diethanolamino]-1,3,5- triazin-2-Y1]-amino}-stilbene-2,2-disulfonic acid.

The brightener compounds of this invention may be applied to substratescomprised of cellulose, polyamides, and proteinaceous fibers, and othersubstrates, from dilute aqueous solutions.

The compounds of this invention are generally employed in their saltform, however, the acid fonn may be isolated if desired.

The compounds which 1 have discovered are particularly advantageous notonly because of the high degree of brightness which they impart tofabrics, but because the fabrics substantially maintain their brightappearance even after treatment with cationic fabric softeners. As hasbeen mentioned before, the brighteners currently on the market aremasked or quenched when the fabrics containing them are subsequently orsimultaneously treated with cationic softeners.

The application of the brighteners of this invention to fabrics ca. 1 beeffected by conventional methods well known to the art. The fabric canbe padded with the brightener during the manufacture at the mill, or inthe more familiar manner, the brightener may be incorporated intodetergent compositions and thus be applied to the fabric during thelaundry operation. Furthermore, the brighteners of this invention can beincorporated into cationic softener compositions and thus applied to thefabric at the same time the softener is applied. Generally, an aqueoussolution of from about 0.05 to about 2 percent of brightener compound isemployed.

Typical cationic softeners on the market are dialkyl dimethyl ammoniumchloride solutions in which the alkyl groups generally are 12-18 carbonatoms in length. The alkyl groups in some formulations may beethoxylated. lMethyl-lalkylamidoethyl-2-alkyl-imidazolinium methosulfatetype softeners are representative of other cationic softeners alsoavailable.

The compounds of this invention can be combined with commerciallyavailable detergents. Typical detergent formulations comprise:

Compound Amount by Weight Linear Alkylbenzene Sulfonate 20% SodiumTripolyphosphate 50% Sodium Metasilicate 5% Sodium Sulfate 15%Carboxymethyl-cellulose 0.8% Moisture, etc. 9.2%

The compounds of this invention and their starting materials can beprepared readily by conventional procedures familiar to those skilled inthe art.

Thus in one manner of preparation, 2 moles of cyanuric chloride arefirst reacted with 1 mole of diaminostilbenedisulfonic acid and theresulting intermediate in turn is reacted with 2 moles of aniline, ormetanilic or sulfanilic acid, and then with 2 moles of the appropriateamine.

The preparation can also be accomplished by the reaction of thedichlorodianilino compound 4,4'-bis-[(6-anilino-4- chloro-l ,3,5-triazin-2-Yl )-amino ]-stilbene-2 ,2-disulfonic acid with theappropriate amine.

The following examples describing certain representative embodiments ofthis invention will serve to further illustrate the nature of theinvention. It is to be understood that the examples are merelyillustrative and intended to enable those skilled in the art to practicethe invention in all of the embodiments flowing therefrom and do not inanyway limit the scope of the invention defined in the claims.

EXAMPLE 1 A slurry of 150 grams of 4,4-bis-[(6-anilino-4-chloro- 1 ,3,5-triazin-Z-Yl)-amino]-stilbene-2,2'-disulfonic acid in 1,200 ml of waterwas prepared. To this slurry 71 grams of N-(3aminopropyl)-diethanolamino are added with stirring and the mixtureheated to 90 C. The pH decreased to 9.5 10 and thereafter was maintainedat 10.5 1 1 by the addition of 16 grams of 50 percent sodium hydroxide.The reaction mixture was then cooled to room temperature. The motherliquor was decanted, and 1,200 ml of water and 300 grams sodium chlorideadded. The solids were ground in a wet slurry with 400 ml of percentsodium chloride solution and acidified to pH 2 with 37 percenthydrochloride acid. The mixture was refiltered, washed free of mineralacid and dried in vacuo at 60 C. Yield 120 grams of a light yellowsolid. The resultant product is 4,4'-bis 4-anilino-6-[N-(3-aminopropyl)- diethanolamino]- l ,3 ,5-triazin-2-Y1}-amino}-stilbene-2,2'- disulfonic acid.

EXAMPLE 2 After decanting mother liquors in Example 1 above, 60 grams ofthe semi-solid mass were dissolved in 240 ml of water and 150 ml ofisopropyl alcohol at 50 C. At 45-50 C the mixture was added dropwise to3.5 liters of rapidly agitated concentrated isopropyl alcohol (20-25 C).The mixture was filtered. washed with 1 liter conc. isopropyl alcoholand sucked dry. it was then dried in vacuo at C initially, then at 60 C.Yield: 115 grams ofa very light yellow powder.

EXAMPLE 3 276 grams of water and 300 grams of ice were placed in a flaskand 70 grams of cyanuric chloride and 66 grams of sulfanilic acid added.The mixture was stirred for 1 hour at 0 C. After 3 hours a dropwiseaddition of 269 grams of 15 percent sodium carbonate was accomplished,bringing the pH to 7. At the end of the addition, 1,052 grams of 6.46percent diaminostilbenedisulfonic acid/Na CO solution were added all atonce. The mixture was heated to 70 C and a pH 8 8.5 maintained.Thereafter the temperature was raised to 90 95 C, and 400 ml of hotwater and 125 grams sodium chloride added; followed by seeding. Then themixture was air cooled to C and filtered.

All of the wet filter cake is mixed with 72.2 grams N(3- aminopropyl)diethanolamine and 75.2 grams triethanol amine and a slurry is obtainedin one-half hour at room temperature. The temperature is raised to 90 95C and the mixture agitated at this temperature for 1 hour, then cooledto C, and 96.4 grams of ethyl cellosolve added with 100 ml water.Thereafter the mixture is filtered through a filter aid. The resultantproduct is 4,4'-bis{ 4 su1foanilino-6-[N-(3-aminopropyl)-diethano1amino]- l ,3,5-triazin-2-Yl ]-amino}- stilbene-2,2disulfonic acid triethanol amine salt solution.

EXAMPLE 4 The procedure of Example 1 is repeated but the N-(3-aminopropyl)diethanolamine is replaced with N,N-d imethyl-1,3-propanediamine. The resultant product is 4,4-bis{ 4- anilino6-[N,N-dimethy1-1,3-propanediamino]-1,3,5-triazin- 2-Y1]-amino}-stilbene-2,2'-disulfonic acid.

EXAMPLE 5 The procedure of Example 1 is repeated but the N-(3-aminopropyl)-diethanolamine is replaced with 4-(3-aminopropyl)morpholine. The resultant product is 4,4-bis{[4-anilino-6-[4-(3-aminopropy1)morpho1ino]- l ,3,5-tria2in-2- Y1I-amino}-sti1bene-2,2'-disu1fonic acid.

EXAMPLE 6 The procedure of Example 1 is repeated but the N-(3-aminopropyl)-diethanolamine is replaced with (3,3-diamino-N-methyldipropylamine). The resultant product is 4,4'-bis{[4-ani1ino-6-[(3,3 '-diamino N-methy1dipropylamino)]-1,3,5- triazin-2-Yl]-amino}-stilbene-2,2'-disulfonic acid.

EXAMPLE 7 Softener formulations were made up using the brighteners ofExample 1, 4, 5, and 6. Each formulation was comprised of:

5 ml triethanolamine 10 ml methyl cellosolve 31 ml water 4 gmsdistearyl-dimethyl ammonium chloride 160 mg ofa brightener compound ofthis invention. The pH of each formulation was adjusted to 5 with aceticacid.

A. 20 Gram samples of unmercerized cotton fabric were washed in aTerg-O-Tometer washer with 600 ml of water for 10 minutes at F using 1gram of unbrightened anionic detergent. The fabric was then rinsed for 2minutes in 600 ml of water.

" B. Thereafter the fabrics were rinsed for 10 minutes in theTerg-O-Tometer at 100 F with 0.6 grams of the above softener formulationin 600 ml of water. The Lumetron and Hunter Values were then determined.

The following table illustrates the degree of brightness imparted to thefabric by the compounds of this invention in the presence of cationicsofteners.

Additional batches of softener formulations were made with thebrightener compounds of Examples 1, 4, 5, and 6 in the same manner asExample 7; the pH was again adjusted to 5, this time with formic acid.

20 Gram samples of unmercerized, prewet, unwashed cotton were thenrinsed in the Terg-O-Tometer for 10 minutes at 100 F with 0.6 grams ofsoftener formulation in 600 m1 of water.

Thereafter the Lumetron and Hunter values of each sample were detemiinedand are shown in Table 2.

TABLE 2 Softener formu- Flourescence lation with compound (Lumetron ofexample value) Hunter Values The foregoing examples clearly demonstratethe high degree of brightness that is imparted to fabric treated withthe brighteners of this invention. This high degree of brightness isvery surprising when found on fabrics which have been treated with acationic fabric softener.

While the invention has been explained by detailed descrip tion ofcertain specific embodiments, it is understood that variousmodifications and substitutions can be made in any of them within thescope of the appended claims which are intended also to includeequivalents of such embodiments.

What is claimed is:

1. A composition of matter consisting essentially of an anionic-alkylbenzene sulfonate detergent and an effective amount of a brightenercompound of the formula:

wherein 1 has a value of 0 or 1;

X and Y are each an hydroxyethyl group of taken together form amorpholino ring. B. alkaline salts of A. 2. A composition of matter asclaimed in claim 1 wherein the brightener compound is 4,4'-bis4-anilino-6-[N-(3- aminopropyl)-diethanolamino]-1 ,3,5-triazin-2-Yl]-amino}- stilbene-2,2'disulfonic acid or an alkaline salt thereof.

3. A composition of matter consisting essentially of a cationic fabricsoftener and an effective amount of a brightener compound of theformula:

wherein 1 has a value of 0 or 1;

X and Y are each an hydroxyethyl group or taken together form amorpholino ring.

B. alkaline salts of A.

4. A composition of matter as claimed in claim 3 wherein the brightencrcompound is 4,4-bis 4-anilino-6-[N-(3-aminopropyl)-diethanolamino]-1,3,5-triazin-2-Yl ]-amino}stilbene-2,2'-disulfonic acid or an alkaline salt thereof.

5. A composition of matter as claimed in claim 3 wherein the softener isa dialkyl dimethyl ammonium chloride said alkyl group containing 12 to18 carbon atoms and the brightener compound is 4,4'-bis{[4-anilino-6-[N-( 3- aminopropyl)-diethanolamino -l ,3,5-triazin-2Yl]-amino} stilbene-2,2'disulfonic acid or an alkaline salt thereof.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTIONPATENT NO. I DATED July 11, 1972 INV ENTOR(S) Christopher JohannesTscharner It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

On t he cover sheet, .Assignee, Geigy Chemical Corporation" should readCiba-Geigy Corporation Column 3, line 1 "diethanolamino"should readdiethanolamine Signed and Scaled this Twenty-first Day of February I 978[SEAL] Attest:

RUTH C. MASON LUTRELLE F. PARKER Attesting Oflicer Acting Commissionerof Patents and Trademarks

2. A composition of matter as claimed in claim 1 wherein the brightenercompound is 4,4''-bis ((4-anilino-6-(N-(3-aminopropyl)-diethanolamino)-1,3,5-triazin-2-Yl)-amino)-stilbene-2,2''disulfonic acid or an alkaline salt thereof.
 3. Acomposition of matter consisting essentially of a cationic fabricsoftener and an effective amount of a brightener compound of theformula:
 4. A composition of matter as claimed in claim 3 wherein thebrightener compound is 4,4''-bis ((4-anilino-6-(N-(3-aminopropyl)-diethanolamino)-1,3,5-triazin-2-Yl)-amino)-stilbene-2,2''-disulfonic acid or an alkaline salt thereof. 5.A composition of matter as claimed in claim 3 wherein the softener is adialkyl dimethyl ammonium chloride said alkyl group containing 12 to 18carbon atoms and the brightener compound is 4,4''-bis( (4-anilino-6-(N-(3-aminopropyl)-diethanolamino)-1,3, 5-triazin-2Yl)-amino)-stilbene-2,2''disulfonic acid or an alkaline salt thereof.